US4242278AExpiredUtility

Process for the preparation of 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones

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Assignee: CIBA GEIGY CORPPriority: Mar 31, 1977Filed: Oct 3, 1978Granted: Dec 30, 1980
Est. expiryMar 31, 1997(expired)· nominal 20-yr term from priority
Inventors:Pierre MartinHans GreuterEginhard SteinerDaniel Bellus
C07C 61/15C07C 53/50C07C 45/67C07C 61/40C07C 51/62C07C 51/60C07C 45/45
60
PatentIndex Score
4
Cited by
8
References
21
Claims

Abstract

A process for the preparation of 2-(2',2',2',-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula ##STR1## in which one of the radicals R 1 and R 2 is methyl and the other is hydrogen or methyl, or R 1 and R 2 together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, comprising reacting a 2,4,4,4-tetrahalogenobutyric acid chloride in the presence of an organic base with an ethylene compound which is disubstituted in 1-position by the radicals R 1 and R 2 , as defined above, to form a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one and then rearranging the latter, in the presence of a catalyst, into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the above formula; said 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones being valuable intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid and its insecticidally active esters; as well as the 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the above formula and the intermediates utilized for their preparation.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A process for the preparation of a 2-(2'-2'-2'-tri-halogenoethyl)-4-halogenocyclobutan-1-one of the formula I ##STR26## in which one of the radicals R 1  and R 2  is methyl and the other is hydrogen or methyl, R 1  and R 2  together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, which comprises reacting, at a temperature of from about 0°-200° C., a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II ##STR27## in which X and Y are as defined under formula I, in the presence of an organic base with an olefin of the formula III ##STR28## in which R 1  and R 2  are as defined under formula I, said base and said olefin being, respectively, present in at least equimolar amounts relative to said acid chloride, to give a 2-(2',2',2-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV ##STR29## in which R 1 , R 2 , X and Y are defined under formula I, and then rearranging the latter, in the presence of about 0.1 to 15%, by weight of said butane-1-one, of an acid, base or quaternary ammonium halide catalyst, into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I; said rearrangement being conducted at a temperature of from about 60°-150° C. when in a melt system and at a temperature of 0°-150° C. when in an inert organic solvent system.   
     
     
       2. A process according to claim 1, which comprises using 2,4,4,4-tetrachlorobutyric acid chloride as the 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II. 
     
     
       3. A process according to claim 1, which comprises using 2-chlor-4,4,4-tribromobutyric acid chloride of the formula II. 
     
     
       4. A process according to claim 1, which comprises using an olefin of the formula III in which one of the radicals R 1  and R 2  is methyl and the other is hydrogen or methyl, or R 1  and R 2  together are an alkylene group having 2 to 3 carbon atoms. 
     
     
       5. A process according to claim 1, which comprises using isobutylene as the olefin of the formula III. 
     
     
       6. A process according to claim 1, which comprises using methylenecyclopropane as the olefin of the formula III. 
     
     
       7. A process according to claim 1, which comprises carrying out the reaction of a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II with an olefin of the formula III in the presence of pyridine or of a trialkylamine having 1 to 4 carbon atoms in each alkyl group and in the presence of an inert organic solvent. 
     
     
       8. A process according to claim 1, which comprises carrying out the reaction of a 2,4,4,4-tetrahalogenobutyric acid chloride of the formula II with an olefin of the formula III in the presence of triethylamine. 
     
     
       9. A process according to claim 1, which comprises using an inorganic or organic proton acid as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       10. A process according to claim 1, which comprises using a hydrogen halide acid as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4- halogenocyclobutan-1one of the formula I. 
     
     
       11. A process according to claim 1, which comprises using an organic base as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       12. A process according to claim 1, which comprises using an amine of the formula ##STR30## in which Q 1  is alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, benzyl or phenyl and Q 2  and Q 3  independently of one another are hydrogen or alkyl having 1 to 8 carbon atoms, as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       13. A process according to claim 1, which comprises using a salt of a proton acid with ammonia, a nitrogen-containing organic base or a quaternary ammonium salt as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       14. A process according to claim 1, which comprises using a salt of a hydrogen halide acid with an aliphatic, cycloaliphatic, araliphatic or aromatic primary, secondary or tertiary amine or a heterocyclic nitrogen base as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       15. A process according to claim 1, which comprises using a salt of the formula ##STR31## in which M is fluorine, bromine or iodine and especially chlorine, Q 4  is hydrogen, alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl and Q 5 , Q 6  and Q 7  independently of one another are hydrogen or alkyl having 1 to 18 carbon atoms, or a N-alkylpyridinium halide having 1 to 18 carbon atoms in the alkyl group, as the catalyst for the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I. 
     
     
       16. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-cyclobutan-1-one of the formula I at temperatures of between 80° and 130° C. 
     
     
       17. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-cyclobutan-1-one of the formula I in the melt at a temperature of between 80° and 130° C. in the presence of a trialkylamine having 1 to 8 carbon atoms in each alkyl group or of a tetraalkylammonium halide having 1 to 18 carbon atoms in the alkyl groups. 
     
     
       18. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I in the presence of an inert solvent. 
     
     
       19. A process according to claim 1, which comprises carrying out the rearrangement of a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I in an aliphatic alcohol having 1 to 4 carbon atoms, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol, diethyl ether or diisopropyl ketone, as the solvent. 
     
     
       20. A 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one of the formula IV ##STR32## in which one of the radicals R 1  and R 2  is methyl and the other is hydrogen or methyl, or R 1  and R 2  together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine. 
     
     
       21. A 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the formula I ##STR33## in which one of the radicals R 1  and R 2  is methyl and the other is hydrogen or methyl, or R 1  and R 2  together are alkylene having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine.

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